EP3713414B1 - Sac de stockage d'aliments, insecticide, hermétique, son utilisation et son procédé de fabrication - Google Patents

Sac de stockage d'aliments, insecticide, hermétique, son utilisation et son procédé de fabrication Download PDF

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Publication number
EP3713414B1
EP3713414B1 EP17801043.5A EP17801043A EP3713414B1 EP 3713414 B1 EP3713414 B1 EP 3713414B1 EP 17801043 A EP17801043 A EP 17801043A EP 3713414 B1 EP3713414 B1 EP 3713414B1
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EP
European Patent Office
Prior art keywords
layer
textile
bag
polymer
multilayer film
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EP17801043.5A
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German (de)
English (en)
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EP3713414A1 (fr
Inventor
Mikkel Vestergaard Frandsen
Thomas Weis
Allan MORTENSEN
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Vestergaard Sarl
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Vestergaard Sarl
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D29/00—Sacks or like containers made of fabrics; Flexible containers of open-work, e.g. net-like construction
    • B65D29/02—Sacks with laminated or multiple walls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B—MAKING CONTAINERS OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B70/00—Making flexible containers, e.g. envelopes or bags
    • B31B70/74—Auxiliary operations
    • B31B70/79—Coating; Impregnating; Waterproofing; Decoating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B—MAKING CONTAINERS OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B2155/00—Flexible containers made from webs
    • B31B2155/003—Flexible containers made from webs starting from tubular webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B—MAKING CONTAINERS OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B2160/00—Shape of flexible containers
    • B31B2160/10—Shape of flexible containers rectangular and flat, i.e. without structural provision for thickness of contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
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    • B31B2170/00—Construction of flexible containers
    • B31B2170/20—Construction of flexible containers having multi-layered walls, e.g. laminated or lined
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions

  • the present invention relates to a hermetic, insecticidal food storage bag, use of it and a method for its production.
  • the bag is used for post-harvest crop storage, especially in the form of sacks.
  • Pest infestation by insects and fungi is a widespread problem, especially during storage of the crop in sacks. Therefore, pesticides are sometimes used during storage, for example by directly treating grains in sacks, for example by using fumigation. However, consumption of pesticides may imply a health hazard for the consumer.
  • US patent US3859121 by Yeaden discloses impregnated textile bags for the storage and transport of food and feed, like grains
  • US4966796 by Sumitomo discloses a kraft paper grain storage bag with pyrethroid for protection of grains
  • European patent application EP382382 by Imperial Chemical discloses impregnated woven or non-woven fabric, for example as sacks for foodstuff.
  • Multilayer material is discussed in British patent application GB 1568936 by Heselev , disclosing packaging material for food, for example brown rice, where insecticide is incorporated in a polymer film, for example part of a laminate.
  • US2014/0037706 by ProvisionGard Holding discloses a packaging structure for human and animal food, for example a bag for grain storage or dog food.
  • the packaging structure comprises a film that contains a pest control agent, for example juvenile hormones, and which is coated onto a polymer weave, for example in order to prevent insects boring through the material.
  • the layer with the active agent can be on the inside or the outside of the bag. Coating is potentially done by extrusion.
  • the packaging material comprises a polypropylene (PP) film on a PP weave.
  • 0.7 mm oriented polypropylene is disclosed, covering a layer if Linear Low Density Polyethylene (LLDPE) with a pest control agent (containing hormones) on top of a PP weave.
  • the pest control agent can be added directly to the extruder.
  • EP1325070 by Proctor & Gamble discloses extrusion-coating a hydrophilic, vapor permeable, water impermeable, film-layer onto a substrate, for example a textile or fabric substrate. Insecticide is mentioned as an option for an active agent in the film. A possible use is for food packaging or article for agriculture.
  • a film bag is made of multiple layers.
  • the multiple layers of the film bag comprise an airtight layer, an insect barrier layer comprising an insecticide or insect repellent, and a chemical barrier layer for limiting permeation of the insecticide or insect repellent through the chemical barrier layer into the crop inside the bag. This way, the grains inside the bag are not exposed to the insecticide.
  • the airtight layer has the effect of killing the insects by suffocation, which has the further significant effect of helping to delay the onset of resistance to the insecticide or insect repellent.
  • the low oxygen levels within the airtight bag can also prevent or slow down the growth of mold.
  • an insect attempts to penetrate the storage bag, it penetrates the chemical barrier layer and comes into contact with the insecticide or insect repellent.
  • the film bag optionally inserted into an outer robust bag, potentially containing a rodent repellent.
  • Purdue University has published studies on crop storage bags called Purdue Improved Crop Storage (PICS) bags which is also subject to various reports and articles, which can be found on the Internet, including Wikipedia and the Purdue internet site https://www.entm.purdue.edu/PICS2/project_overview.php , both of which contain various literature references.
  • a PICS bag has a size for 50-100 kg grains and consists of two layers of 80 micron thick polyethylene liners and a third layer made from woven polypropylene. When each layer is tied and closed separately, it creates a hermetically sealed environment for storing harvested grain.
  • Suffocation is also discussed in US6063418 by Sugimoto et al. and assigned to Fujimori Kogyo Ltd, disclosing a container with an outer high-strength PP 1500 deniers flat yarn woven bag, which contains an inner bag that has a low CO2 permeation level, suitable for being filled with CO2 for suffocating the insects inside the inner bag.
  • An example of the inner bag is a five-layer structure of a 10 micron thick EVOH layer sandwiched between two 5 micron thick adhesive layers and two 30 micron thick LLDPE layers.
  • rodents are a severe problem for crop storage because rodents damage the sacks for storage when biting through the material. For this reason, a variety of substances have been proposed for protection of crops, including castor oil, capsaicin, and denatonium saccharide.
  • An objective of the invention to provide an improvement in the art.
  • An objective is a low-cost, light-weight food storage bag which provides an efficient barrier against insects that are trying to enter the bag from outside and which, at the same time, prevents breeding inside the storage bag by insects from pre-infestation, potentially even kills the insects inside the bag.
  • the bag is especially useful for crop storage, for example storage of grains.
  • a typical form of the bag is a flexible sack of a size typically used for grain storage, for example for a weight in the range of 20-100 kg.
  • the method and principles set forth in the following can also be used for a flexible large scale transport bag for storage of larger quantities, for example in the range of 100-2000 kg.
  • the general principle of the invention is to provide a textile bag made of a textile material, typically high-strength textile material, which is extrusion-coated or laminated with a multilayer film that comprises insecticide in addition to a hermetic layer that prevents oxygen from entering the bag, as permeation of oxygen through the multilayer film is prevented.
  • This oxygen barrier suffocates and/or dehydrates the insects inside the bag, and the insecticide kills insects that try to bore through the bag from the outside.
  • extrusion-coating is understood as a coating of the textile by attaching a molten multilayer polymer stream directly onto the textile surface and then solidifying the multilayer stream to become a multilayer film.
  • laminate is herein understood as a prefabricated multilayer film that is bonded onto the textile, typically by a molten bonding polymer between the textile and the multilayer film.
  • insects is used herein for simplicity in a broad sense, covering various arthropods in connection with infection of foodstuff, especially crops, such as grain. Accordingly, the term “insect” should be understood as not limited to the Insecta class but also other arthropod classes, especially Arachnida, of which particular interest has the sub-class Acari, which contains mites. In relation to foodstuff protection, also lice are included in the term "insect”.
  • insecticide should thus also be understood in a general sense for not only killing insects but also killing acaricides.
  • insect repellent is to be understood as repelling insects, including acari and lice, but not killing them. Thus, the insects are able to stay alive and move away when exposed to the insect repellent.
  • a hermetic insecticidal crop storage textile bag is provided with an inner side facing an inner volume and an opposite outer side facing the environment, wherein the bag comprises a textile sheet forming the bag with an outer side covered with a polymer multilayer film provided by extrusion-coating or lamination onto the textile.
  • the multilayer film comprises an insecticidal layer of a first thermoplastic polymer containing an active agent, which is at least one of insecticide and insect repellent, for preventing intrusion of insects into the bag by the insecticidal layer. Furthermore, the multilayer film also comprises an oxygen barrier layer made of a second thermoplastic polymer, wherein the oxygen barrier layer has an oxygen permeability sufficiently low for preventing breeding of potential insects inside the bag, and preferably killing potential insects inside the bag.
  • oxygen barrier is used for a polymer layer that has an oxygen permeability of less than 100 ccm/m2/day per 25 microns thickness layer (25 ⁇ m ⁇ 1 mil).
  • oxygen permeability of the oxygen barrier is less than 60 ccm/m2/25 ⁇ m/day or even less than 1 ccm/m2/25 ⁇ m/day, the latter being fulfilled by EVOH.
  • polyamide (PA) film has a permeability of 40 ccm/m2/day, which implies that a PA film with a thickness of 25 microns has an OTR of 40 ccm per square meter of the foil per day.
  • a PET film has a permeability of 55 ccm/m2/day, which implies that a PET film with a thickness of 25 microns has an OTR of 55 ccm per square meter of the foil per day.
  • Ethylene vinyl alcohol, EVOH has a permeability of 0.3 ccm/m2/25 ⁇ m/day, which is two orders of magnitude lower.
  • the oxygen permeability in the same units for PP and HDPE is 2325 and for LLDPE as high as 6800.
  • the first group is regarded as oxygen barrier materials, whereas the second group is not.
  • the OTR for a single layer PICS bag was measured to 490 ccm/m2/day. A double layer would correspond to half of that, yielding 245 ccm/m2/day. From the reports of prevented breeding for a single PICS and expectedly better killing effect for a double layer PICS bag, it is reasonable to assume that a killing effect and proper effect against breeding is obtained for an OTR of less than 300 ccm/m2/day. This accounts for bags with a size in the range of 20-100 kg.
  • an OTR of less than 300 ccm/m2/day is obtained with a PA or PET layer having a thickness of less than 4 or 5 microns, respectively.
  • An oxygen barrier of PA or PET with a thickness of 5 microns appears sufficient from this perspective.
  • the oxygen barrier layer thickness of 5 microns is advantageous for low weight while still being sufficiently stable during co-extrusion.
  • the multilayer film is thinner than the 80 microns that are used for the PICS bags that were described above. This is especially so because the multilayer film is combined with the textile, which adds to the stiffness of the bag.
  • the multilayer film has a maximum thickness of only 50 microns. As will be discussed later, experiments were made with multilayer films thinner than this. However, in order to achieve a low OTR, a layer of a polymer suitable as oxygen barrier is added to the multilayer film.
  • the insecticidal polymer has a greater layer thickness than the oxygen barrier, especially, if the oxygen barrier is EVOH, as this is the most efficient oxygen barrier material among the above polymers.
  • the thickness of an EVOH oxygen barrier typically, is much less than 25 microns.
  • the thickness of the EVOH layer was 5 microns, which was found fully sufficient for barrier properties of a typical sack for grain storage as well as for larger bag-containers.
  • higher OTR can be acceptable. If a suitable limit for the OTR is less than 100 ccm/m2/day, a 25 micron layer of PET or PA would be sufficient. If the criteria is an OTR of less than 50 ccm/m2/day, a PA layer of 25 microns with an OTR of 40 ccm/m2/day would suffice for this purpose as well as a PA layer of 30 microns.
  • PET is not advantageous over EVOH with respect to oxygen permeability and weight, however, when using a PET fabric, a PET layer in the extrusion-coated film, where the PET layer is facing the PET fabric, has advantages with respect to binding without the need of bonding layers, in contrast to PA, PE, and PP, which typically need a bonding layer in order to get attached to a PET textile.
  • PET material has a substantial cost advantage over EVOH and also over PA.
  • the low cost and easy access to PET through PET recycling may favor use of PET in the multilayer, especially when the textile is also made of PET, even though the weight as compared to a multilayer with only EVOH as the barrier would increase.
  • the insecticidal layer can be of different polymer, for example PP or PE, optionally LDPE or LLDPE.
  • the insecticidal film is provided on the outer side of the textile in order to kill insects before they bore a way through the textile.
  • a further advantage for the film only being on the outer side of the textile is a simple and low-cost production. The latter is valid, especially, if the textile is provided as a seamless tube of textile that is subsequently coated.
  • the textile is provided as an endless textile web, for example woven using thin polymer flat tapes as yarns, optionally PP, HDPE, or PET yarns.
  • Typical widths of the flat tapes are in the range of 2-4 mm for storage sacks and in the range of 3-6 mm for big-bags.
  • the weaving for a textile web is normally done in a circular loom, which produces an endless tubular textile web.
  • the textile By providing the textile as a closed tube, especially woven tube, no seaming is needed along the web, which simplifies the production method. Also, the lack of longitudinal seam along the web results in higher strength, which, in turn, allows a thinner material to be used. This reduces weight and costs of the textile.
  • the crop storage bag comprises a tubular polymer textile with a seam only at the bottom or comprises a seam only at the bottom as well as at the top, once both ends of the bag are closed with such seams.
  • the tubular textile web is flattened into a flat two-layer textile web with two opposite outer sides, and the web is rolled onto rollers.
  • the flattened web is then later unrolled from the roller and laminated with a multilayer film covering the textile surface.
  • the flattened textile is extrusion-coated with a molten multilayer polymer stream that solidifies into a multilayer film, once on the textile.
  • the advantages of the production as described herein are higher production speed, simpler production, less consumption of material, lower cost, lower weight, easier transport and easier handling by the end user.
  • the bag combines the principle of an insecticidal barrier against intruding insect with the principle of hermetic suffocation and/or dehydration of the insects inside the bag. This way, breeding is prevented and advantageously, the insects are killed. Due to the low cost and low weight in combination with an efficient crop protection, the bag is highly suitable for crop protection in countries where low cost is essential for selection of post-harvest crop protection.
  • the second thermoplastic polymer for the oxygen barrier is different from the first thermoplastic polymer for the insecticidal layer, for example as described above for the EVOH, PET or PA barrier layer combination with PP or PE insecticidal layer.
  • the multilayer film with the oxygen barrier is provided between the textile web and the insecticidal first polymer layer for protecting the oxygen barrier by the insecticidal first polymer layer, especially if the latter has a greater thickness than the oxygen barrier.
  • the insecticide or insect repellent is configured for migrating in the insecticidal first polymer to the surface of the multilayer film for release thereof.
  • the active agent is selected among insecticides and insect repellents that are capable of migrating in the insecticidal first polymer to the surface of the multilayer film for release of the active agent.
  • the active agent and the one or more additional polymer layers have to be selected such that active agent can migrate from the insecticidal first polymer layer through the one or more additional polymer layers and to the outer surface of the coated bag.
  • a rodent repellent is potentially added to the first polymer and melt-incorporated therein or provided in an additional outer polymer layer or applied to the outer surface of the multilayer film as a coating, for example an impregnation.
  • the method comprises extrusion-coating the web with the multilayer stream, wherein the extrusion coating comprises melting the insecticidal first polymer and the second polymer for the oxygen barrier in an extruder and co-extruding a multi-layer molten stream with the two layers of first and second polymer, and optionally further layers, for example bonding layers.
  • the multilayer film with the insecticidal first polymer layer and the oxygen barrier layer is then combined with the web while the multilayer film from the extruder is still in a molten state or at least partially molten state.
  • the combination of the multilayer stream and the textile is done before the molten multilayer film from the extruder is solidified.
  • Extrusion-coating has the advantage of a faster process with less energy consumption as compared to solidifying the multilayer stream first into a multilayer film, rolling the multilayer film onto a roller, and then bonding it with a molten bonding layer for lamination onto the web.
  • the method comprises providing the multilayer film with a width that is larger than the web in order for the multilayer films extending outside opposite edges of the flattened web, for example extending 2-5 mm on either side, and in order to fuse face-to-face along and outside both edges of the web, thus, providing a tight sealing along opposite edges of the flattened web.
  • These additional method steps result in a crop storage bag, wherein the multilayer film, when the bag is in collapsed flattened condition, has a width that is larger than the width of the textile and extends a distance beyond opposite edges of the polymer textile, where the multilayer films from opposite sides of the flattened bag are fused face-to-face into a tight sealing of the bag.
  • the multilayer film is provided on the textile with an overlap in order to provide proper sealing.
  • a good material for the oxygen barrier is EVOH, as it has a very low oxygen permeability and, thus, can be used efficiently even at low thickness of only a few microns, for example 3-10 microns, optionally 3-5 microns.
  • the layer of the insecticidal first polymer, for example PE or PP is thicker, for example in the range of 5-20 microns, optionally 10-15 microns
  • the multi-layer film is provided as a four-layer structure with an inner bonding layer towards the textile web on one side of the EVOH, and a second bonding layer on the opposite side of the EVOH for bonding the EVOH to the PE or PP.
  • an EVOH oxygen barrier with an insecticidal first polymer layer of a polyolefin, for example PE or PP has proven advantageous because the extrusion temperatures of the EVOH and the PE or PP are similar. Therefore, this combination of materials is good for co-extrusion of the multilayer film, potentially with some additional bonding layers, also called tie-layers, in between, for example on either side of the EVOH layer.
  • useful tie-layers can be made from modified ethylene acrylate resins, for example as marketed under the name of Bynel ® from the company DuPont ® . Examples include Bynel ® 22E757 or 21E830, the latter being an anhydride modified ethylene acrylate resin.
  • a co-extrusion temperature of in the range of 200-270° has proven useful for EVOH and PE or PP.
  • a relatively low extrusion temperature is desired, in particular for insecticide or insect repellents that disintegrate easily and quickly at high temperatures.
  • a temperature sensitive pyrethroid especially deltamethrin (DM)
  • low temperatures are beneficial.
  • An example of the multilayer film and potentially multilayer stream is a four-layer structure with an inner bonding layer towards the web on one side of the EVOH, and a second bonding layer on the opposite side of the EVOH for binding the EVOH to the insecticidal first polymer layer of PE or PP.
  • An insecticidal first polymer layer of 15 micron thick PP was provided in the multilayer film in combination with a 5 micron thick EVOH that was sandwiched between two tie-layers of the same thickness.
  • the total thickness was 30 microns, roughly corresponding to a weight of 30 g/m2.
  • the insecticidal first polymer layer as an outer layer was provided as PP with 0.3% by weight DM, incorporated in the PP while in a molten state inside the extruder.
  • the multilayer was extrusion coated onto a tubular PP flat-yarn woven textile having a weight of 55 g/m2.
  • the concentration of the insecticide, optionally DM is in the range of 0. 1-10% by weight of the first polymer to which the insecticide is added.
  • insecticide and/or insect repellent and potentially rodenticide are melt-incorporated in the first polymer of the insecticidal layer, which potentially is also an outer layer and facing the environment, unless covered by further outer polymer layers.
  • the active agent is added to the first polymer while the first polymer is in a molten state.
  • the active agent is added to the extruder before or during extrusion.
  • it is incorporated in a polymer masterbatch which is then melting a second time in the final extruder for the multilayer stream.
  • the polymer and the insecticide and/or repellent and optional rodenticide are selected such that the active agent is capable of migrating from inside a bulk of the polymer to the surface of the polymer from which it is released.
  • the migration of the active agent to the surface of the bag is hampered by a covering of the insecticidal layer with an additional outer polymer film layer, through which the insecticide is not migrating or only migrating at a small rate. Even this configuration, still yields protection against insects that try to penetrate the insecticidal layer on their way from outside the bag into the inner volume of the bag.
  • An advantage of an additional outer polymer film layer, through which the insecticide is not migrating or only migrating at a small rate, is a reduction of the risk for health issues for humans caused by contact with insecticide on the outer surface of the bag.
  • An additional outer polymer film layer covering the insecticidal layer where the additional outer polymer film layer has a blocking effect against migration of the active agent or has reduced migration properties, potentially, increases the lifetime of the insecticidal efficacy of the insecticidal layer because the insecticide is kept concentrated in the insecticidal layer underneath the additional outer polymer film layer.
  • the insecticidal layer acts as a reservoir for the insecticide which is confined by the additional outer polymer film layer.
  • the additional outer polymer film layer is a Biaxially Oriented PP (BOPP) film layer, potentially with a printing thereon.
  • BOPP Biaxially Oriented PP
  • Such BOPP layer typically, has reduced migration properties as compared to an extruded insecticidal PP layer due to the oriented polymer achieved by stretching the BOPP film in two directions.
  • the BOPP layer is not entirely blocking migration of pyrethroid, such as DM, it is useful not only for prolonging the lifetime of the insecticide but also for providing an insecticidal outer surface.
  • the additional outer polymer film layer comprises a print.
  • Such print comprises typically colors, pictures and/or alphanumeric information.
  • information includes at least one of indicators and information about use, content, and/or producer of the bag.
  • Adding an additional outer polymer film layer can be done by multiple principles as described in the following.
  • a multilayer stream comprising an oxygen barrier polymer layer and insecticidal polymer layer is extrusion-coated onto the textile and solidified on the textile into a multilayer film, potentially with the oxygen barrier between the insecticidal layer and the textile.
  • an additional outer polymer film layer is laminated, for example with an extruded bonding layer (tie layer) between the insecticidal first polymer layer and the additional outer polymer film layer.
  • a multilayer stream comprising an oxygen barrier layer and insecticidal first polymer layer is extruded and solidified into a multilayer film, which is later laminated onto the textile, for example with an extruded bonding layer (tie layer) between the multilayer film and the textile.
  • an additional outer polymer film layer is laminated, for example with an extruded bonding layer (tie layer) between the insecticidal first polymer layer and the additional outer polymer film layer.
  • a multilayer stream comprising an oxygen barrier layer and insecticidal first polymer layer, is extruded and used as a molten lamination bonding layer for the additional outer polymer film layer.
  • the additional outer polymer film layer is without insecticide or insect repellant.
  • the additional outer polymer film layer optionally can be provided with an additional active agent, for example an additional insecticide and/or additional insect repellent.
  • an oxygen scavenger is provided inside the bag on or in the textile or even remote from the textile.
  • the oxygen scavenger is potentially iron (Fe) based.
  • the oxygen absorber is multi-functional, for example absorbing oxygen and releasing CO2. The oxygen absorber absorbs oxygen inside the bag, causing a faster suffocation and/or dehydration and also preventing mould to grow.
  • thermoplastic polymers for the textile are not only polyolefins, such as PE or PP, but also useful is polyethylene terephthalate (PET, polyester). Instead of a woven textile, a knitted or non-woven textile can also be used.
  • insecticides include pyrethrin and synthetic pyrethroids, for example deltamethrin and permethrin, and, alternatively, quinazolines, fiproles, pyroles, pyrazoles, neonicotinoids, carbamates. Concentrations in the range of 1ppm and 10% are dependent on the insecticide and the desired release speed. To the insecticides can be added synergists, for example piperonyl butoxide (PBO). For deltamethrin, typical concentrations are in the range of 1-10 g/m2
  • repellents for the insect repellent source are oil of wintergreen, garlic, lime, citronella, black pepper, chili pepper, capsaicin & its derivatives, geraniol, catnip (napeta lactone), sandalwood, eugenol, lippia multifloria (verbena), neem, cajeput (Melaleuca Leucadendron), lemongrass (Cymbopogon Flexuosus), cedar (Cedrus Deodora), peppermint (Mentha Piperita), java citronella (Cymbopogon Winterianus), clove (Syzygium Aromaticum), geranium (Pelargonium Graveolens), rosemary (Rosmarinus Officinalis), and sesame (Sesamum Indicum).
  • rodent repellents examples include capsaicin and denatonium saccharide. Concentrations in the range of 1ppm and 10% by weight of the polymer are dependent on the type of rodenticide and the desired strength and release speed.
  • the active agent in order to prolong the efficacy of the insecticide and/or repellent, is provided on a support particle from which it is gradually released into the first polymer for migration to the surface of the first polymer.
  • support particles have a sub-micron size or a micron size range of only a few microns, for example in the range of 1-5 microns.
  • An example for support particles for the repellent/insecticide is nanoclay. Examples of nano-clays are attapulgite and montmorillonite.
  • micro-particles or nano-particles are used, for example ground natural minerals or synthetic material, including silica, alumina and silicates.
  • support particles for active agents include also kaolin, talc, chalk, quartz, carbon black, diatomaceous earth, calcite, marble, pumice, sepiolite and dolomite.
  • Polymer based sponge-like particles can also function as the support for repellent.
  • Example of foodstuff includes cocoa, coffee, rice, beans, and grains, including maize, wheat, and barley.
  • Additives may be incorporated into the first polymer, for example UV protectors, colorants, optical brighteners, fillers, reinforcement fibres, flame retardants, anti-soiling agents, further biocides, and/or fragrance.
  • FIG. 1 illustrates a bag 1 with a tubular polymer sheet material 2 that has a closed bottom 3.
  • the bottom 3 has been provided by flattening the tubular material 2 and closing an end part 4 of it, for example by welding, gluing, sewing, or a combination of one or more of these.
  • the bag 1 has an upward opening 5 that is open and ready for filling foodstuff into the bag 1, for example crop products, such as grains or rice.
  • a cross section 6 is shown enlarged to the right of the bag 1, although, not to scale.
  • the sheet material 2 of the bag 1 comprises a textile 7 and a thermoplastic polymer multilayer film 8 coated onto the outer side of the textile 7.
  • the textile 7 is tubular, coating the outer side of the tubular textile 7 is much easier than coating the inside. This will become more apparent below when examples are given for production processes.
  • the textile 7 is a weave of the type where flat yarns are interwoven.
  • Such flat yarns are typically produced by extruding a thermoplastic polymer film, typically stretching the film for orienting the polymer for increased strength, and cutting the film into narrow strips, for example with a width in the range of 3-5 mm, which are then rolled onto bobbins from which they are later used for weaving.
  • polymer materials are polyolefins, for example polyethylene (PE) or polypropylene (PP).
  • PE include High Density PolyEthylene (HDPE), Low Density PolyEthylene (LDPE), or Linear Low Density PolyEthylene (LLDPE), and mixtures thereof.
  • Alternatives include polyester (PolyEthylene Terephtalate, PET). The list is not exhaustive.
  • FIG. 1 also an example of a coating is illustrated, where the coating is a multilayer polymer film 8 with an outer insecticidal layer 9 that also add strength to the bag 1.
  • Useful polymers for the insecticidal layer 9 are polyolefins, optionally PP and PE, for example LDPE or LLDPE.
  • EVOH ethylene vinyl alcohol
  • PA polyamide
  • the oxygen barrier 10 is, optionally, sandwiched between bonding layers 11, 11', also called tie-layers. Further additional layers are possible, however, the simple four layer structure has proven useful and sufficient.
  • FIG. 2 illustrates a possible production process for the textile 7.
  • a weaving station 12 flat yarns 13 are supplied from a plurality of bobbins 14 for weaving of the tubular woven textile 7.
  • the tubular textile 7 is collapsed into a double layered flattened structure 15.
  • a typical material for the flat yarns is a polyolefin, for example PP or PE, although, also PET is a good candidate.
  • the textile 7 is provided at a separate location than the coating and, therefore, rolled onto rollers 16, which are then transported to the coating location and unrolled as needed.
  • a knitted or non-woven tubular textile is also a possibility.
  • the multilayer film is co-extruded as a multilayer stream and cooled for solidification, potentially stretched for orientation of the polymer, and then rolled onto rollers. In a subsequent step, the film is rolled off the rollers and laminated onto the weave.
  • the multilayer film 8 is co-extruded as a multilayer stream and, while the film 8 from the extruder is still in a molten or partially molten state, laid onto the textile 7 where it solidifies.
  • This process is typically called extrusion-coating.
  • This method is simpler in that it avoids a solidification process of the multilayer film 8 after co-extrusion, the rolling of the multilayer film 8 onto rollers, possible transport of the rollers, and a subsequent lamination process.
  • FIG. 3 illustrates such extrusion-coating process as part of an exemplified production.
  • the production is as follows.
  • a multilayer co-extruder system 17 is provided, which in the exemplified case comprises three screw-extruders 17A, 17B, 17C.
  • One extruder 17A is used for the two tie layers 11, 11', one extruder 17B for the polymer of the oxygen barrier 10, for example EVOH, and one extruder 17C containing the polymer for the insecticidal first polymer layer 9, for example PP or PE.
  • the molten polymers from the three extruders 17A, 17B, 17C are combined by coextrusion into a molten multilayer stream 8' of the type as illustrated in FIG.
  • the extruded multilayer stream 8' keeps its multilayer structure until it in molten or partially molten state is laid down on the flattened structure 15 as a coating, bonded to the textile 7, and solidified as a multilayer film 8 on the textile 7.
  • a similar extruder system 17 is provided further downstream.
  • the final material 2 is a tubular woven textile 7 with a multilayer film 8 covering the outer surface of the textile 7.
  • the multilayer stream 8' is still in molten or partially molten state, it can be used as a bonding layer for one or more additional outer polymer layers 25, for example a printed BOPP layer.
  • such one or more additional outer polymer layers 25 are laminated onto the final multilayer film 8 in a subsequent step, for example with an additional bonding layer in between.
  • This method can also be used in connection with the embodiment of FIG. 4b , although not illustrated.
  • FIG. 4a illustrates an alternative process, in which a multilayer film 18 is extruded as a multilayer stream 18', potentially stretched for orientation of the polymer, and after cooling and solidification in a cooling step 20, rolled onto rollers 19.
  • the multilayer film 18 in FIG. 4a does not comprise the bonding layer 11' that is used to bond the multilayer film 18 of FIG. 4a to the textile 7.
  • FIG. 4b illustrates a subsequent step, in which the multilayer film 18 without the inner bonding layer 11' is rolled off the rollers 19 and laminated onto the textile 7 by adding the still molten or partially molten bonding layer 11' from the extruder 17' between the multilayer film 18 and the flattened structure 15 of the textile 7. Also, this process is used on both sides of the flattened structure 15, which comprises two layers of textile 7.
  • an outer polymer layer for example a printed BOPP layer, or several layers is/are laminated onto the textile (7) in a subsequent step after having laminated the multilayer film (8) onto the textile.
  • FIG. 5a illustrates the textile 7 with the multilayer film 8 from a top view. It is observed that the multilayer film 8 comprises an overlay 8A that extends beyond the edge 15A of the flatted structure 15 of the textile 7. This makes sure that there is a tight bonding of the multilayer film 8 along and around the textile 7.
  • the flattened structure 15 is cut along predetermined transverse paths 21.
  • FIG. 5b illustrates one way of closing the bottom 3, where a fold 22 is provided at the end part 4 which is fixed for providing a sealed bottom 3 of the bag 1.
  • the outermost film layer 9 being a polyolefin, especially PE or PP, it is ultrasound or heat weldable for a proper sealing.
  • Alternative or additional sealing includes sewing or gluing.
  • FIG. 5c illustrates an alternative closure of the end part 4 where a sealing strip 23 is folded over the bottom part of the sheet material 2 across the entire sheet material 2 and then sealed against the polymer sheet material 2 of the bag 1 in order to provide a sealed bottom 3, for example by at least one of welding, gluing and sewing.
  • the sealing strip 21 is typically a polymer film, for example PE or PP, which is weldable against at least the outer first polymer layer 9 of the multilayer film 8.
  • FIG. 5d illustrates an even further closure of the end part 4, wherein a welding 24, for example ultrasonic welding or heat welding, is provided through and across the double layer flattened structure 15, where the welding fuses the two textile 7 layers of the double layer flattened structure 15, typically including the multilayer film 8.
  • a welding for example ultrasonic welding or heat welding
  • the active agent in the outer insecticidal layer 9 is added to the extruder prior to extrusion of the polymer.
  • insecticides examples include pyrethroids, optionally permethrin or deltarangin (DM).
  • EVOH is advantageous, when combined in the multilayer film 8 with an insecticidal layer 9 of PE or PP because the necessary extrusion temperatures for EVOH and PA or PP are similar.
  • PA has a higher extrusion temperature, which makes the process not only more difficult, but which also increases the temperature of the PE or PP, which can be detrimental for the insecticide in such layers.
  • DM is heat sensitive.
  • extrusion temperatures of the PE or PP multilayer film with EVOH is in the range of 250-270°C in order to provide good adhesion to the textile 7, for example PE or PP weave.
  • An improvement has been found by heating the textile 7 to a temperature of 70-80 degrees so that the cooling of the extruded multilayer stream 8' into a multilayer film 8 is slowed down.
  • the extrusion temperature can be lowered to 220-250°C for PP as the insecticidal first polymer layer or to 200-230°C for PE, optionally LDPE. Both ranges are suitable for EVOH as well.
  • the lower temperature is beneficial for insecticide in the insecticidal first polymer layer, especially pyrethroids, such as DM, which is heat sensitive and quickly degrades at such elevated temperatures. It should be noticed that such temperatures are not suitable for PA extrusion, as PA need a much higher extrusion temperature, why EVOH also from this standpoint is superior to PA as an oxygen barrier when combined with PE or PP.
  • the overall weight of the film 8 was about 30 g/m2, which is much less than the thickness of 60 micron and weight of 60g/m2 of the prior art liner that is inserted into an outer strength giving woven bag.
  • insecticide and/or insect repellent and optionally rodenticide in the outer insecticidal layer 9, an efficient barrier was provided against insects and potentially rodents which are attempting to make their way through the bag material 2.
  • the stability is higher than a bag with a seam along the side of the bag. Furthermore, the coating adds to the stability of the textile, why also the textile could be made thinner than in the prior art where the complete bag is provided as a double bag with an outer strength-giving textile bag and an oxygen barrier as an inner film bag.

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Claims (18)

  1. Procédé de fabrication d'un sac textile hermétique de stockage de cultures insecticides (1), le sac comprenant un côté interne faisant face à un volume interne et un côté externe opposé faisant face à l'environnement, dans lequel le procédé comprend la fourniture au sac d'une couche textile formant le côté interne du sac, dans lequel le textile est tissé, tricoté ou non tissé, et la fourniture au sac (1) d'un film multicouche de polymère (8, 18) uniquement sur le côté externe ; dans lequel le film multicouche (8) comprend une couche de polymère insecticide (9) dans laquelle un insecticide est incorporé à l'état fondu pour empêcher l'intrusion d'insectes dans le sac (1) par la couche de polymère insecticide (9) ;
    caractérisé en ce que
    le procédé comprend l'inclusion d'au moins une couche de polymère barrière à l'oxygène (10) dans le film multicouche (8, 18) pour fournir un taux de transmission d'oxygène, OTR, à travers le film multicouche (8) suffisamment bas pour empêcher la reproduction ou la mort d'insectes potentiels à l'intérieur du sac (1) lorsque le sac (1) est à l'état fermé.
  2. Procédé selon la revendication 1, dans lequel le procédé comprend la fourniture au film multicouche d'un OTR inférieur à 300 ccm/m2/jour.
  3. Procédé selon la revendication 1, dans lequel le procédé comprend la fourniture d'une feuille de textile (7) pour le sac et soit le revêtement par extrusion d'un flux multicouche (8') de polymère fondu sur le textile (7) et la solidification du flux en film multicouche (8) soit la stratification du film multicouche (18) sur le textile.
  4. Procédé selon la revendication 2, dans lequel le procédé comprend les étapes consistant à fournir la feuille de textile sous la forme d'une bande sans fin de textile (7), à aplatir la bande de textile (7) en une bande de textile plate à deux couches (15) avec deux côtés extérieurs opposés, et à recouvrir les deux côtés extérieurs avec le film multicouche (8, 18) par laminage ou par extrusion-revêtement ; dans lequel la couche insecticide (9) est fournie par un premier polymère thermoplastique, et la couche barrière à l'oxygène (10) est fournie par un second polymère thermoplastique qui est différent du premier polymère thermoplastique ; dans lequel le procédé comprend l'orientation du film multicouche (8, 18) avec la barrière à l'oxygène (10) entre la nappe textile (7) et la première couche de polymère insecticide (9) pour protéger la barrière à l'oxygène (10) par la première couche de polymère insecticide (9).
  5. Procédé selon la revendication 3, dans lequel le procédé comprend la fourniture de la nappe textile sans fin (7) sous la forme d'une nappe textile tubulaire sans soudure et le revêtement du film multicouche (8, 18) sur la nappe, puis la découpe (21) de la nappe en parties, chaque partie pour un sac, et enfin la fermeture d'une extrémité (4) de la partie pour fournir à un sac (1) une couture fermée (22, 23, 24) uniquement au fond (3) ou enfin la fermeture des extrémités opposées de la partie pour fournir à un sac (1) une couture fermée (22, 23, 24) au fond (3) et au sommet du sac (1) mais pas de couture sur un côté du sac (1) à partir du fond vers le sommet.
  6. Procédé selon la revendication 3 ou 4, dans lequel le procédé comprend la fourniture du film multicouche (8, 18) avec une largeur qui est supérieure à la nappe aplatie (15) afin que les films multicouches (8, 18) soient fusionnés sur des côtés opposés de la nappe le long et à l'extérieur des deux bords (15A) de la nappe pour fournir une fermeture étanche le long de la nappe.
  7. Procédé selon une quelconque revendication précédente, dans lequel le procédé comprend la fourniture de la barrière à l'oxygène (10) sous la forme d'une couche d'éthylène alcool vinylique, EVOH, et la première couche de polymère insecticide (9) sous la forme d'une couche de polyéthylène ou de polypropylène, la première couche de polymère insecticide (9) ayant une plus grande épaisseur que la couche barrière à l'oxygène (10).
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel le revêtement du film multicouche (8) est fourni soit sous la forme d'un processus de stratification qui comprend la fusion du premier et du second polymère dans une extrudeuse (17) et la co-extrusion des deux couches (9, 10) faisant partie d'un flux multicouche (18'), le refroidissement du flux multicouche (18') pour former un film multicouche (18) et l'enroulement du film multicouche (18) sur des rouleaux (19) ; au niveau de l'emplacement de stratification, l'enroulement du film multicouche (18) à partir du rouleau et sa stratification sur le textile (7) ; la stratification d'une couche de film polymère externe supplémentaire (25) sur le film multicouche (18), qui comprend une impression de surface mais pas d'insecticide, ou en tant que processus de revêtement par extrusion qui comprend la fusion du premier et du second polymère dans une extrudeuse (17) et la coextrusion des deux couches (9, 10) en tant que partie d'un flux multicouche (8') ; et la stratification d'une couche de film polymère externe supplémentaire sur le textile (7) avec le flux multicouche (8') en tant que matériau de liaison entre la couche de film polymère externe supplémentaire et le textile (7), tandis que le flux multicouche (8') est toujours à l'état partiellement ou totalement fondu ; puis la solidification du flux multicouche (8') en un film multicouche (8) tandis qu'il est sur le textile (7) et recouvert par la couche de film polymère externe supplémentaire (25).
  9. Procédé selon une quelconque revendication précédente, dans lequel le procédé comprend la sélection de l'insecticide pour la couche insecticide parmi des insecticides capables de migrer dans le premier polymère thermoplastique.
  10. Procédé selon une quelconque revendication précédente, dans lequel l'insecticide est la deltaméthrine ou la perméthrine.
  11. Sac textile hermétique de stockage de cultures insecticides (1) avec un côté interne faisant face à un volume interne et un côté externe opposé faisant face à l'environnement, dans lequel le sac (1) comprend une couche textile (7) formant le côté interne du sac, dans lequel le textile est tissé, tricoté ou non tissé, et avec un côté externe recouvert d'un film multicouche de polymère revêtu par extrusion ou stratifié (8, 18), le film (8, 18) comprenant une couche insecticide (9) d'une première couche de polymère thermoplastique (9) contenant un insecticide pour empêcher l'intrusion d'insectes dans le sac par la couche insecticide ; caractérisé en ce que le film multicouche (8, 18) comprend également au moins une couche barrière à l'oxygène (10) constituée d'un second polymère thermoplastique afin que le film multicouche (8) avec la couche barrière à l'oxygène (10) ait un taux de transmission de l'oxygène, OTR, suffisamment bas pour empêcher la reproduction ou la mort d'insectes potentiels à l'intérieur du sac (1) lorsque le sac (1) est à l'état fermé.
  12. Sac textile selon la revendication 11, dans lequel l'OTR est inférieur à 300 ccm/m2/jour à la pression atmosphérique.
  13. Sac textile selon l'une quelconque des revendications 11 à 12, dans lequel la couche barrière à l'oxygène (10) est située entre la nappe textile (7) et la première couche de polymère insecticide (9) pour protéger la couche barrière à l'oxygène (10) par la première couche de polymère insecticide (9) ; dans lequel le premier polymère insecticide contient l'insecticide incorporé à l'état fondu.
  14. Sac textile selon l'une quelconque des revendications 11 à 13, dans lequel le premier polymère est le PE ou le PP et le second polymère est l'EVOH, dans lequel la première couche de polymère insecticide (9) a une épaisseur supérieure à la couche barrière à l'oxygène d'EVOH (10).
  15. Sac textile selon la revendication 13 ou 14, dans lequel l'insecticide est capable de migrer dans le premier polymère thermoplastique.
  16. Sac textile selon l'une quelconque des revendications 11 à 15, dans lequel le film multicouche (8) est recouvert d'une couche de film polymère extérieure supplémentaire (25) comprenant une impression de surface mais pas d'insecticide.
  17. Sac textile selon l'une quelconque des revendications 11 à 16, dans lequel l'insecticide est la deltaméthrine ou la perméthrine.
  18. Utilisation d'un sac selon l'une quelconque des revendications 11 à 17 pour le stockage de produits de cultures, par exemple des céréales.
EP17801043.5A 2017-11-21 2017-11-21 Sac de stockage d'aliments, insecticide, hermétique, son utilisation et son procédé de fabrication Active EP3713414B1 (fr)

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PCT/EP2017/079877 WO2019101289A1 (fr) 2017-11-21 2017-11-21 Sac de stockage d'aliments, insecticide, hermétique, son utilisation et son procédé de fabrication

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EP3713414B1 true EP3713414B1 (fr) 2024-01-03

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US (1) US20200353724A1 (fr)
EP (1) EP3713414B1 (fr)
CN (1) CN111372454A (fr)
MX (1) MX2020005253A (fr)
PH (1) PH12020550747A1 (fr)
WO (1) WO2019101289A1 (fr)

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IT202100014189A1 (it) * 2021-05-31 2022-12-01 Sachim Srl Supporto in polietilene cui è legato un idrogel caricato con un principio attivo naturale antiparassitario

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PH12020550747A1 (en) 2021-04-26
CN111372454A (zh) 2020-07-03
MX2020005253A (es) 2020-11-09
EP3713414A1 (fr) 2020-09-30
WO2019101289A1 (fr) 2019-05-31
US20200353724A1 (en) 2020-11-12

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